Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids

ABSTRACT

The invention relates to a make-up solution for a galvanic bath comprising organometallic components, a wetting agent, a complexing agent and free cyanide, wherein the make-up solution further comprises copper in the form of copper II cyanide and potassium, and complex indium allowing, after addition of alkaline aurocyanide, to galvanically depositing a gold alloy.

This is a Divisional Patent Application of U.S. patent application Ser. No. 12/678,984 filed on Mar. 18, 2010, which is a National Phase Application in the United States of International Patent Application PCT/EP 2008/062042 filed Sep. 11, 2008, which claims priority on Swiss Patent Application No. 01494/07 of Sep. 21, 2007. The entire disclosures of the above patent applications are hereby incorporated by reference.

The invention relates to an electrolytic deposition in the form of a thick gold alloy layer and the manufacturing method thereof

In the field of decorative plating, methods are known for producing gold electrolytic depositions that are yellow with a fineness greater than or equal to 9 carats, ductile with a thickness of 10 microns, and with a high level of tarnish resistance. These depositions are obtained by electrolysis in an alkaline galvanic bath containing 0.1 to 3 g/1 of cadmium, in addition to gold and copper. The depositions obtained via these known methods have however cadmium levels of between 1 and 10%. Cadmium facilitates the deposition of thick layers, i.e. between 1 and 800 microns and provides a yellow alloy by reducing the quantity of copper contained in the alloy, however, cadmium is extremely toxic and prohibited in some countries.

Other known yellow depositions are alloys comprising gold and silver.

18 carat gold alloys containing copper and zinc and no cadmium are also known. However, these depositions are too pink (fineness too copper rich). Finally, these depositions have poor resistance to corrosion which means that they tarnish quickly.

It is an object of this invention to overcome all or part of the aforementioned drawbacks by proposing a method for depositing a thick gold alloy layer that is yellow and has neither zinc nor cadmium as main components.

The invention thus relates to an electrolytic deposition in the form of a gold alloy, whose thickness is comprised between 1 and 800 microns and includes copper, characterized in that it includes indium as the third main component.

According to other advantageous features of the invention:

-   -   the deposition is substantially free of toxic metals or         metalloids;     -   the deposition includes a colour comprised within the fields of         1N and 3N (in accordance with ISO standard 8654);     -   the deposition is shiny and is highly resistant to corrosion.

The invention also relates to a method for the galvanoplasty deposition of a gold alloy on an electrode dipped in a bath including gold metal in the form of aurocyanide alkaline, organometallic components, a wetting agent, a complexing agent and free cyanide, characterized in that the alloy metals are copper in the form of the copper II cyanide and potassium, and indium in complex aminocarboxylic or aminophosphoric form for depositing a shiny reflective? yellow type gold alloy.

According to other advantageous features of the invention:

-   -   the bath includes from 1 to 10 g·l⁻¹ of gold metal in the form         of alkaline aurocyanide;     -   the bath includes from 30 to 80 g·l⁻¹ of alkaline copper II         cyanide;     -   the bath includes from 10 mg·l⁻¹ to 5 g·l⁻¹ indium metal in         complex form;     -   the bath includes 15 to 35 g·l⁻¹ of free cyanide;     -   the wetting agent in the bath includes a concentration of         between 0.05 to 10 m·l⁻¹;     -   the wetting agent is selected from among polyoxyalkylenic, ether         phosphate, lauryl sulphate, dimethyldodecylamine-N-oxide,         dimethyl-dodecyl ammonium propane sulfonate types or any other         type able to wet in an alkaline cyanide medium;     -   the aminocarboxylic complexing agent includes a concentration of         between 0.1 and 20 g·l⁻¹;     -   the bath includes an amine in a concentration of between 0.01         and 5 ml·l⁻¹;     -   the bath includes a depolarising agent in a concentration of         between 0.1 mg·l⁻¹ and 20 mg·l⁻¹;     -   the bath includes conductive salts of the following types:         phosphates, carbonates, citrates, sulphates, tartrates,         gluconates and/or phosphonates;     -   the temperature of the bath is maintained between 50 and 80° C.;     -   the pH of the bath is maintained between 8 and 12;     -   the method is carried out at current densities of between 0.2         and 1.5 A·dm⁻².

The electrolysis is preferably followed by a thermal treatment at at least 450 degrees Celsius for at least 30 minutes in order to obtain optimum deposition quality.

The bath may also contain a brightener. The brightener is preferably a butynediol derivative, a pyridinio-propane sulfonate or a mixture of the two, a tin salt, sulfonated castor oil, methylimidazole, dithiocarboxylic acid, such as thiourea, thiobarbituric acid, imidazolidinthione or thiomalic acid.

In an example deposition, there is a gold alloy, free of toxic metals or metalloids, in particular free of cadmium, with a 2N yellow colour, a thickness of 200 microns, excellent brilliance and highly wear and tarnish resistant.

This deposition is obtained by electrolysis in an electrolytic bath of the following type:

Example 1

-   -   Au: 3 g·l⁻¹     -   Cu: 45 g·l⁻¹     -   In: 0.1 g·l⁻¹     -   KCN: 22 g·l⁻¹     -   pH: 10.5     -   Temperature: 65° C.     -   Current density: 0.5 A·dm⁻²     -   Wetting agent: 0.05 ml·l⁻¹ NN-Dimethyldodecyl N Oxide     -   Iminodiacetic: 20 g·l⁻¹     -   Ethylenediamine: 0.5 ml·l⁻¹     -   Potassium selenocyanate: 1 mg·l⁻¹

Example 2

-   -   Au: 6 g·l⁻¹     -   Cu: 60 g·l⁻¹     -   In: 2 g·l⁻¹     -   KCN: 30 g·l⁻¹     -   NTA: 4 g·l⁻¹     -   Ag: 10 mg·l⁻¹     -   Diethylentriamine: 0.2 ml·l⁻¹     -   Gallium, selenium or tellurium: 5 mg·l⁻¹     -   Sodium hypophosphite: 0.1 g·l⁻¹     -   Thiomalic acid: 50 mg·l⁻¹     -   Current density: 0.5 A·dm⁻²     -   Temperature: 70° C.     -   pH: 10.5     -   Wetting agent: 2 ml·l⁻¹ ether phosphate

In these examples, the electrolytic bath is contained in a polypropylene or PVC bath holder with heat insulation. The bath is heated using quartz, PTFE, porcelain or stabilised stainless steel thermo-plungers. Proper cathodic agitation and electrolyte flow must be maintained. The anodes are made of platinum plated titanium, stainless steel, ruthenium, iridium or alloys thereof

Under such conditions, cathodic efficiency of 62 mg·A·min⁻¹ can be obtained, with a deposition speed of 1 μm in 3 minutes in example 1 and, in example 2, a shiny deposition of 10 μm in 30 minutes.

Of course, this invention is not limited to the illustrated example, but is capable of various variants and alterations which will be clear to those skilled in the art. In particular, the bath may contain negligible quantities of the following metals: Ag, Cd, Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi.

Moreover, the wetting agent may be of any type able to wet in an alkaline cyanide medium. 

1. A make-up solution for a galvanic bath comprising organometallic components, a wetting agent, a complexing agent and free cyanide, wherein the make-up solution further comprises copper in the form of copper II cyanide and potassium, and complex indium allowing, after addition of alkaline aurocyanide, to galvanically depositing a gold alloy.
 2. The make-up solution according to claim 1, wherein the complex indium is of the aminocarboxylic or aminophosphonic type.
 3. The make-up solution according to claim 2, wherein the aminocarboxylic complexing agent includes a concentration of between 0.1 mg·l⁻¹ to 20 g·l⁻¹.
 4. The make-up solution according to claim 1, wherein the make-up solution includes from 30 to 80 g·l⁻¹ of copper II metal in the form of alkaline cyanide.
 5. The make-up solution according to claim 1, wherein the make-up solution includes from 10 mg·l⁻¹ to 5 g·l⁻¹ of complex indium metal.
 6. The make-up solution according to claim 1, wherein the make-up solution includes from 15 to 35 g·l⁻¹ of free cyanide.
 7. The make-up solution according to claim 1, wherein the wetting agent includes a concentration of between 0.05 and 10 ml·l⁻¹.
 8. The make-up solution according to claim 7, wherein the wetting agent is chosen from among the following types: polyoxyalkylenic, ether phosphate, lauryl sulphate, dimethyldodecylamine N oxide, dimethyldodecyl ammonium propane sulfonate.
 9. The make-up solution according to claim 1, wherein the make-up solution includes an amine concentration of between 0.01 and 5 ml·l⁻¹.
 10. The make-up solution according to claim 1, wherein the make-up solution includes a depolarising agent in a concentration of between 0.1 mg·l⁻¹ to 20 mg·l⁻¹.
 11. The make-up solution according to claim 1, wherein the make-up solution includes conductive salts of the following types: phosphates, carbonates, citrates, sulphates, tartrates, gluconates, and/or phosphonates.
 12. A Galvanic bath wherein it comprises a make-up solution according to claim 1 and gold in the form of alkaline aurocyanide allowing to galvanically depositing a shiny reflective yellow type gold alloy.
 13. The galvanic bath according to claim 12, wherein the galvanic bath includes from 1 to 10 g·l⁻¹ of gold metal in the form of alkaline aurocyanide.
 14. The galvanic bath according to claim 12, wherein the galvanic bath includes a metal chosen in the group consisting of Ag, Cd, Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be and Bi as fourth fewer weight concentration of metal in the galvanic bath.
 15. The galvanic bath according to claim 14, wherein the metal chosen is silver and has a concentration of 10 mg·l⁻¹ of silver metal in the galvanic bath. 